The invention relates to a compound polynary micro-electrolysis filler applied in the field of industrial polluted wastewater treatment, and a preparation method thereof. The filler is prepared from, by weight, 40-55 parts of active carbon powder, 20-40 parts of iron powder, 10-20 parts of aluminum powder, 1-3 parts of rhodium powder or ruthenium powder, 15-20 parts of clay and a proper amount of an additive. The preparation method of the filler comprises the following steps: mixing the active carbon powder, the iron powder, the aluminum powder, the rhodium powder or the ruthenium powder, and the clay in proportion, preparing spherical particles, and roasting at a high temperature to obtain the filler. The particle size of the compound polynary micro-electrolysis filler prepared in the invention is 5-10mm. The compound polynary micro-electrolysis filler has the advantages of large specific surface area, high amount of porosity, no passivation, no hardening, reduction of the chemical oxygen demand (COD) and the chroma of wastewater in a short time, and improvement of the biodegradability of the wastewater, has an especially substantial chroma removal effect on the wastewater, and can efficiently treat high-chroma wastewater, such as printing and dyeing wastewater and pharmacy wastewater.